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51.
Rui Tao Xue-Jiao Yin Ke-Hu Wang Yu-Zhuo Niu Ya-Lin Wang Dan-Feng Huang Ying-Peng Su Jin-Xian Wang Yu-Lai Hu Ying Fu Zheng-Yin Du 《中国化学快报》2015,26(8):1046-1049
Exceedingly fast preparation of trifluoromethyl tertiary alcohols has been accomplished from methyl ketones and trifluoromethyl ketones under solvent free conditions by cross Aldol reaction. The reaction was achieved in the presence of common inorganic base by grinding method at ambient temperature to give β-trifluoromethyl-β-hydroxyl ketones in high yields (up to 95%). 相似文献
52.
Lewis Acid Catalyzed Condensation–Cyclization Cascade: Direct Synthesis of Di/Trifluoromethyl‐1,2,3,4‐tetrahydroquinazolines 下载免费PDF全文
Prof. Dr. G. K. Surya Prakash Dr. Attila Papp Socrates B. Munoz Nathan May John‐Paul Jones Prof. Dr. Ralf Haiges Prof. Dr. Pierre Mothé Esteves Dr. Thomas Mathew 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(28):10170-10178
Condensed heterocycles such as quinazolines constitute the framework of many promising drugs. The great impact of the dramatic fluorine effect in pharmaceuticals prompted a great surge in the quest for fluorinated drug design resulting in over 20 % fluorine‐containing drugs in the market today. Therefore, finding an efficient and cost‐effective method for the direct synthesis of fluorine‐tagged quinazoline systems is of great significance in the pharmaceutical arena. For the first time, a one‐pot sequential condensation–cyclization reaction to form selectively the difluoro/trifluoromethylated tetrahydroquinazolines from simple components difluoro/trifluoroacetaldehyde hemiacetal and aromatic amines is reported. Our recent studies using difluoro/trifluoroacetaldehyde hemiacetal as simple and elegant difluoro/trifluoromethyl synthons and metal triflates such as gallium triflate as safe and stable Lewis acid catalysts led us to this direct synthesis protocol for the expedient and convenient synthesis of fluorinated quinazolines. DFT calculations at PCM/B3LYP/6‐31++G** were carried out for evaluating a possible reaction mechanism for this cyclization. According to the DFT calculations, product stereochemistry is thermodynamically driven, favoring the cis isomer as the major product, which is also confirmed experimentally. 相似文献
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54.
从热力学角度研究了酸度、湿度、水的存在状态不同时,单质铜在空气中生成碱式碳酸铜的电动势及其自由能变。通过计算发现:在酸性条件下,p H的大小对于反应的自发性没有影响;大气中二氧化碳溶解达到饱和时,空气湿度增加,反应的自发性略微增加;相同条件下,水由气态变为液态时,反应的自发性增幅较大。 相似文献
55.
A Strategy to Control the Reactivation of Frustrated Lewis Pairs from Shelf‐Stable Carbene Borane Complexes 下载免费PDF全文
Dr. Yoichi Hoshimoto Takuya Kinoshita Prof. Dr. Masato Ohashi Prof. Dr. Sensuke Ogoshi 《Angewandte Chemie (International ed. in English)》2015,54(40):11666-11671
N‐Phosphine oxide substituted imidazolylidenes (PoxIms) have been synthesized and fully characterized. These species can undergo significant changes to the spatial environment surrounding their carbene center through rotation of the phosphine oxide moiety. Either classical Lewis adducts (CLAs) or frustrated Lewis pairs (FLPs) are thus formed with B(C6F5)3 depending on the orientation of the phosphine oxide group. A strategy to reactivate FLPs from CLAs by exploiting molecular motions that are responsive to external stimuli has therefore been developed. The reactivation conditions were successfully controlled by tuning the strain in the PoxIm–B(C6F5)3 complexes so that reactivation only occurred above ambient temperature. 相似文献
56.
Michele Menotta Sara Biagiotti Laura Streppa Luigia Rossi Mauro Magnani 《Analytica chimica acta》2015
In the present paper we describe an atomic force microscopy (AFM)-based method for the quantitative analysis of FK506 (Tacrolimus) in whole blood (WB) samples. Current reference methods used to quantify this immunosuppressive drug are based on mass spectrometry. In addition, an immunoenzymatic assay (ELISA) has been developed and is widely used in clinic, even though it shows a small but consistent overestimation of the actual drug concentration when compared with the mass spectrometry method. The AFM biosensor presented herein utilises the endogen drug receptor, FKBP12, to quantify Tacrolimus levels. The biosensor was first assayed to detect the free drug in solution, and subsequently used for the detection of Tacrolimus in blood samples. The sensor was suitable to generate a dose–response curve in the full range of clinical drug monitoring. A comparison with the clinically tested ELISA assay is also reported. 相似文献
57.
Facile and Mild Synthesis and Characterization of Some New Diazo Dyes on the Basis of Schiff Bases in the Presence of Nanocrystalline Magnesium Oxide as a Base Catalyst under Solvent‐free Conditions 下载免费PDF全文
In this research, some new diazo dyes including Schiff base have been synthesized by the condensation reaction between ethylenediamine and derivatives of salicylaldehyde containing diazo functional groups in the presence of nanocrystalline magnesium oxide as a solid base catalyst under solvent‐free conditions. Nanocrystalline magnesium oxide has been characterized by XRD, BJH and TEM techniques. The corresponding products have been obtained in excellent yields and high purity. All of the obtained diazo‐Schiff bases are highly colored and can be applicable as useful diazo dyes and characterized by spectroscopy data. 相似文献
58.
Mahdi Mirzaei Hossein Eshghi Mohammad Rahimizadeh Mehdi Bakavoli Maryam M. Matin Minoo Hosseinymehr Hadi Amiri Rudbari Giuseppe Bruno 《中国化学会会志》2015,62(12):1087-1096
A series of α‐aminophosphonates were synthesized through one‐pot condensation of aryl aldehydes, aryl amines and diethyl phosphite in the absence of any catalyst and organic solvents. All the synthesized α‐aminophosphonates were characterized by spectral and elemental analysis and in the case of compound 4j by X‐ray crystallography. Some of these new α‐aminophosphonate derivatives were found to have cytotoxic activity on the cancer cell line DU145 in vitro by the MTT method. 相似文献
59.
60.
In this work, solubility, volumetric and viscosity behavior were studied for the systems containing the environmentally acceptable compounds: liquid poly(ethylene glycol) (PEG200) and three ionic liquids: 1-butyl-3-methylimidazolium dicyanamide ([C4mim][dca]), trihexyltetradecyl phosphonium dicyanamide ([P6,6,6,14][dca]) and 1-hexyl-3-methylimidazolium bis{(trifluoromethyl)sulfonyl}amide ([C6mim][NTf2]). The studies were performed in a temperature range (288.15 to 328.15) K and at a pressure of 0.1 MPa. For the only system that evidenced limited miscibility, namely (PEG200 + [P6,6,6,14][dca]), the temperature-composition phase diagram at 0.1 MPa was determined, mapping the existing one- and two-phase regions. In the homogeneous region of this diagram, densities and viscosities were measured and the excess molar volumes, as well as deviations in viscosity were calculated. For the other two systems, as they are always homogeneous in the temperature ranges of the present work, these measurements and calculations were performed in the full range of compositions. The molecular interactions in the studied systems were scrutinized using the obtained excess molar volumes, deviations of viscosity, as well as Kamlet–Taft parameters of PEG200 and the ionic liquids. In addition, the excess molar Gibbs free energies of activation of viscous flow and the related enthalpies and entropies were calculated and introduced to take into consideration the differences in size of the molecules. 相似文献